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Assume the scalar order parameter can take either sign. The cubic term breaks $m\mapsto -m$ symmetry, and a positive quartic coefficient bounds the Landau free energy below. Stationary points satisfyso, besides the disordered point $m=0$, the possible ordered points areThe disordered point has curvature $A^{\prime \prime }(0)=A_2$ and is locally stable when $A_2>0$. Nonzero stationary points first appear whenThat condition alone does not make them the equilibrium phase: one must compare their free energies.

At a nonzero stationary point, substitute $A_2=-A_{3}m-A_4{m}^2$ to obtainFor an ordered state to coexist with $A(0)=0$, this requiresBoth curvatures at phase coexistence are positive and equal to $2A_3^2/(9A_4)$. The barrier is at $m=-A_3/(3A_4)$. In fact the potential at phase coexistence factorizes:The two distinct minima are therefore explicit, with a finite jump in the order parameter whenever $A_3\ne 0$.

To state the equilibrium inequalities for either sign of $A_3$, put $m=-\mathrm{sgn}(A_3)\rho$ with $\rho \ge 0$. This sign always has lower energy than the opposite sign of equal magnitude. ThenThe bracket's minimum is $A_2/2-A_3^2/(9A_4)$. It follows thatThe favored ordered minimum, when it exists, isThus a first-order phase transition is possible and occurs when the coefficients cross the coexistence relation. There is no continuous transition between $m=0$ and the equilibrium ordered state while $A_3$ remains nonzero and $A_4$ remains finite and positive. The ordered state becomes globally favorable while $A_2$ is still positive, before the disordered curvature can vanish. Although a stationary solution tends to zero at $A_2=0$, it is not the global transition branch. A continuous transition would require eliminating the cubic term, outside the stated $A_3\ne 0$ condition.

The spinodal points clarify the metastable region: for $2A_3^2/(9A_4)<A_2<A_3^2/(4A_4)$ the ordered minimum is metastable; for $0<A_2<2A_3^2/(9A_4)$ the disordered minimum is metastable. At $A_2=0$ the disordered state loses local stability. These local-stability limits should not be mistaken for the first-order transition in a cubic-quartic Landau potential.

Discuss the zero-field phase boundaries, taking $h=0$ and writing $r={\mathcal{A}}_2$, $q={\mathcal{A}}_4$, $s={\mathcal{A}}_6>0$. This qualification matters because a conjugate field generally rounds the zero-field continuous transition. Nonzero stationary points satisfy $r+q{m}^2+s{m}^4=0$.

For $q>0$, the continuous phase transition occurs atOn the $r>0$ side the only stable phase is $m=0$; on the $r<0$ side the equilibrium global minima are $\pm m_0$ with $m_0^2\sim -r/q$. The magnetization therefore grows continuously from zero as $r$ changes sign.

For $q<0$, the first-order phase transition instead occurs while $r$ is positive. At phase coexistence, $m=0$ and $m=\pm m_0$ are equally deep global minimum points. With $a=m_0^2>0$, stationarity and equality of free energies giveEliminating $r$ gives $-q{a}^2/4-s{a}^3/3=0$, henceAt this coexistence value, the sextic even Landau potential factors as $f(m)=s{m}^2(m^2+3q/(4s){)}^2/6\ge 0$. This verifies that the three equal stationary values are global minima. Above this coexistence value of $r$ the disordered phase wins; below it the ordered phase wins, with a finite jump in the phase-selected magnetization. The values $r=0$ and $r=q^2/(4s)$ are the disordered and ordered spinodal points, respectively, not the coexistence boundary: the latter follows from the repeated root of $r+qa+s{a}^2=0$.

The two transition loci meet at the tricritical point,Two independent control parameters such as $T$ and $g$ can tune these two conditions. In a generic local phase diagram their coefficient map has a Jacobian matrix of rank two at the intersection; unspecified functions ${\mathcal{A}}_2(T,g)$ and ${\mathcal{A}}_4(T,g)$ do not by themselves determine the geometric orientation of the boundaries. The sextic term stabilizes this intersection and the negative-quartic first-order side.

Take $b>0$ for a stable quartic Landau free energy. The cubic-term removal in a conserved quartic Landau free energy uses $\varphi =\psi -c/(3b)$ and gives, apart from a constant,For a closed binary fluid mixture, the compositional order parameter has fixed integral. Adding $d\int \varphi$ therefore adds the same constant to every allowed state. Equivalently, in the common-tangent construction for phase coexistence, a linear term changes the tangent slope, hence the chemical potential, by $d$, but leaves the coexistence compositions unchanged. This is why linear composition bias leaves coexistence compositions unchanged; it would not mean an unchanged composition at a fixed externally imposed chemical potential.

In the shifted variable, the binodal compositions are ${\psi }_{\pm }=\pm \sqrt{-a^{\prime }/b}$ for $a^{\prime }<0$. They merge atThe continuous phase transition therefore has the same scalar quartic Landau theory as the symmetric binary fluid mixture, with a shifted critical composition and control parameter. In the mean-field approximation, the composition difference vanishes with order-parameter critical exponent $1/2$. This argument presumes the critical composition lies in the physically accessible composition range; conservation affects the dynamics, not this static phase coexistence construction.

Use the stable parameters $b,\kappa >0$. The bulk stationary points satisfy $f^{\prime }(\varphi )=a\varphi +b{\varphi }^3=0$. For $a<0$, $\varphi =0$ has negative curvature, while the two minima areBoth have $f(\pm {\varphi }_B)=-a^2/(4b)$ and $f^{\prime \prime }(\pm {\varphi }_B)=-2a>0$. To establish minimization at fixed total composition, writeFor mean composition $\bar{\varphi }$ with $|\bar{\varphi }|<{\varphi }_B$, a mixture of the two minima with volume fraction $\lambda =(\bar{\varphi }+{\varphi }_B)/(2{\varphi }_B)$ in the positive phase attains this lower bound in the bulk. Macroscopic slabs have only a subextensive interfacial excess free energy, so the bound is attained per unit volume in the thermodynamic limit. Thus constrained minimization gives phase coexistence in the mean-field approximation; at the endpoints only one phase is needed.

The two equilibrium conditions also follow directly by constrained optimization. Introduce a Lagrange multiplier $\mu$ for $\lambda {\varphi }_{+}+(1-\lambda ){\varphi }_{-}=\bar{\varphi }$ in the mixture's bulk free-energy density. Varying ${\varphi }_{+}$ and ${\varphi }_{-}$ gives $f^{\prime }({\varphi }_{+})=f^{\prime }({\varphi }_{-})=\mu$; varying $\lambda$ gives $f({\varphi }_{+})-\mu {\varphi }_{+}=f({\varphi }_{-})-\mu {\varphi }_{-}$. These equate the chemical potentials and pressures, respectively.

Equivalently, their bulk chemical potentials are both zero and their pressures are equal:These are precisely the conditions of the common-tangent construction for phase coexistence: the horizontal supporting tangent touches both minima. Equal chemical potentials prevent net composition exchange, and equal pressure gives mechanical equilibrium at a flat interface.

The equilibrium magnetization is a global minimum of the Landau free energy. Its candidates are the stationary pointsThus $m=0$, or $x=m^2\ge 0$ is a nonnegative root ofOne retains candidates with nonnegative curvature $f^{\prime \prime }(m)$ and compares their free energies; the candidate with the smallest value is the equilibrium state. Equal global minima describe phase coexistence.

At phase coexistence, the finite ordered global minimum has the same free energy as $m=0$. With $x=m^2>0$ and $f(0)=0$, stationarity and equal values giveSubtracting eliminates $r$:Substitute back to get $r_{\ast }=3b^2/(16c)$, soThe three degenerate equilibrium values at this temperature are $0$ and $\pm m_{\mathrm{jump}}$. A useful global check, avoiding confusion with a spinodal point, is the exact factorizationAll three zeros are therefore global minima. Their curvatures are positive: $f^{\prime \prime }(0)=3b^2/(8c)$ and $f^{\prime \prime }(\pm m_{\mathrm{jump}})=3b^2/(2c)$.

The ordered local minimum first appears on cooling at $r=b^2/(4c)$, where the nonzero stationary roots merge. It becomes globally stable only at $r_{\ast }$; the disordered minimum remains metastable down to $r=0$. These different temperatures distinguish phase coexistence from loss of local stability.

For attractive nearest-neighbour interactions, $J>0$, the transformed model is a ferromagnetic Ising model. In three dimensions and at $T<T_c$, its infinite-volume spontaneous magnetization has two branches. As the effective field crosses zero, the equilibrium mean spin changes discontinuously from a negative value to a positive value. Since $(\partial h/\partial \mu {)}_T=1/2$, varying the physical chemical potential crosses this same first-order phase transition.

The particle-hole-symmetric coexistence line isThe mean Ising spin is a rescaled occupation density. Writing $n=⟨N⟩/V$ for the physical number density,The negative-spin phase is a dilute gas and the positive-spin phase is a dense, liquid-like phase. If the spontaneous spin magnitude at coexistence is $m_0(T)>0$, their number densities areThus the physical order parameter is a density or occupation imbalance, not an actual magnetic moment of these particles. In a closed system with an intermediate mean density, the same transition appears as phase coexistence between the two densities. At $T=T_c$ the density contrast vanishes continuously; above $T_c$, sweeping the chemical potential gives no coexistence jump. A true discontinuity requires the thermodynamic limit; a finite sum over finitely many cells remains analytic.

A phase diagram partitions a space of thermodynamic variables into regions occupied by different equilibrium thermodynamic phases and records the phase coexistence curves between them. For a pure, one-component substance, a pressure–temperature phase diagram gives one point for each pair $(T,p)$. In a single-thermodynamic phase region both controls can vary independently. On a two-thermodynamic phase phase coexistence curve, they obey one relation; at a triple point, both are fixed. These statements assume bulk thermodynamic equilibrium, fixed composition and no additional applied fields.^[ref]

At fixed temperature and pressure, the stable bulk thermodynamic phase minimizes Gibbs free energy for a fixed amount of substance. For a pure substance this is a comparison of chemical potentials on a common normalization. Two candidate thermodynamic phases coexist where ${\mu }_{\alpha }(T,p)={\mu }_{\beta }(T,p)$ and neither is exceeded in stability by a third thermodynamic phase. Differentiating their equality gives the Clapeyron equation. Thus a phase coexistence curve is a locus of equal stability, rather than a trajectory that every heated sample must follow.^[ref]

The following original cartoon uses dimensionless positive coordinates $\theta =T/T_{\ast }$ and $\pi =p/p_{\ast }$, with arbitrary reference scales $T_{\ast },p_{\ast }$. It represents no particular substance and contains no measured data. Stipulate a triple point at $(1,1)$, a liquid-gas critical point at $(3,5)$, and these drawing rules:They specify sublimation, liquid–gas phase coexistence and melting boundaries for the picture. They are not an equation of state, do not predict latent heat or mass density, and do not supply a quantitative critical theory. In particular, the melting slope is merely an illustrative choice.

For example, at fixed $\pi =3$ the melting boundary is at $\theta =1.2$ and the liquid–gas boundary is at $\theta =2$. Heating from $(\theta ,\pi )=(1.6,3)$ to $(3.6,3)$ therefore starts in liquid, crosses phase coexistence at $(2,3)$, and ends in gas. In an equilibrium conversion at that crossing, added heat can change the phase fraction at fixed temperature through latent heat. The pressure–temperature point alone does not specify how much of each thermodynamic phase is present: for that one needs an additional amount or volume constraint.

Now connect exactly the same endpoints by raising $\pi$ from $3$ to $6$ at $\theta =1.6$, moving to $\theta =3.6$ at $\pi =6$, then lowering $\pi$ to $3$. The first leg stays on the liquid side because ${\theta }_{\mathrm{melt}}$ ranges only from $1.2$ to $1.5$ and ${\pi }_{\mathrm{vap}}(1.6)=2.2<3$. The second leg lies above the entire liquid–gas boundary, whose largest drawn pressure coordinate is $5$; the third lies beyond its largest temperature coordinate, $3$. No leg crosses a first-order phase transition boundary. The middle leg passes through a supercritical fluid region, with $\theta >3$ and $\pi >5$, and the final leg returns to a gaslike state continuously.

Avoiding a first-order phase transition does not mean that no heat or work is exchanged. Along the detour, mass density, enthalpy and heat capacity may change substantially but continuously. The liquid-gas critical point itself has singular behavior, so the detour goes around it rather than through it. This connected fluid region is the striking lesson of a phase diagram: a familiar change from liquid to gas need not involve boiling across a sharp boundary.

An equilibrium phase diagram also does not predict how rapidly a conversion occurs. Metastability and a barrier described by classical nucleation theory can delay the observed phase transition. Nor should a binary-composition phase diagram be read as the same picture: its coexistence regions and lever rule encode composition and phase fractions, and can occupy an area even though pure-substance two-thermodynamic phase coexistence occupies a curve in the pressure–temperature plane.

A system can split into macroscopic regions with distinct local order parameters, densities or compositions. In a short-range system at phase coexistence, regions of two phases with means $M_1,M_2$ and volume fractions $q,1-q$ have spatial mean $M=q{M}_1+(1-q)M_2$. Their interface contribution is subextensive, so their thermodynamic free-energy density is the corresponding convex combination of the phase densities. This can lie below the homogeneous-branch Landau free energy at the same $M$. The equilibrium constrained order-parameter free energy is consequently convexified, with a straight coexistence segment described by the Maxwell construction. A nonconvex local potential remains useful for homogeneous branches, metastability and interfaces, but must not be identified with the full equilibrium constrained density throughout a coexistence interval.

A concrete experiment turns the phase coexistence curve into pairs of temperature and saturation pressure. A 1969 paper reports water measurements made in 1942 and 1947–1949 using a boiler and precision mercury manometer. Platinum resistance thermometers read the boiler temperature through a resistance bridge. The pressure-transfer line passed through an ice-water condenser and a dry-ice trap; helium filled connecting sections. Corrected mercury column height gave the pressure at the thermometer coils, including hydrostatic pressure contributions from water vapor, helium, mercury, and mercury vapor.^[ref]

Controls included normal/reversed-lead readings, readings at two thermometer electric currents extrapolated to zero current to remove self-heating, repeated bridge calibration, and daily triple point thermometer calibration checks. Cellar temperature measurements corrected fluid-column and gauge-block thermal expansion. One measurement series was excluded because a trapped gas bubble was suspected of corrupting the mercury head. The paper adjusted measurements to round temperatures using previously tabulated slopes; those adjusted values therefore are not independent measurements of those slopes.^[ref]

The thermodynamic inference requires liquid and gas in phase coexistence, a well-defined common temperature, and a pressure corrected to that same location. Leaks, contamination, or a temperature gradient can spoil that interpretation. A separate calorimetry measurement of latent heat, together with the two specific volumes, allows a test of the full Clapeyron equation. Converting a measured phase coexistence curve slope directly into latent heat instead assumes that equation; it is not an independent test.

Sensible heat is transferred heat associated with a temperature change within a single thermodynamic phase. By contrast, latent heat can change the phase fraction while the temperature stays fixed during equilibrium phase coexistence. Neither name denotes an additional stored substance: both describe how transferred heat participates in a process.

For fixed mass $m$ and composition, use the heat capacity appropriate to the heating constraint. Under the quasistatic process assumptions in heat capacity, with only pressure-volume work and unchanged bulk kinetic energy and potential energy, fixed-pressure heating givesHere $c_p$ is specific heat capacity at constant pressure; fixed-volume heating instead uses specific heat capacity at constant volume $c_V$. A cooling step has negative $Q_{\mathrm{sens}}$ with the sign convention in heat. A temperature difference has the same numerical value in units of the kelvin or degree Celsius. The integral follows by adding the small transfers $\delta Q=m{c}_p(T)dT$, rather than assuming a constant heat capacity.

As a stylized ice-to-water example for a fixed-composition closed system at fixed pressure $1\mathrm{atm}$, take $m=0.5\mathrm{kg}$, an initial temperature of $-10{}^{\circ }\mathrm{C}$, melting at $0{}^{\circ }\mathrm{C}$, and a final temperature of $20{}^{\circ }\mathrm{C}$. Assume constant specific heat capacity at constant pressure values $c_{\mathrm{ice}}=2.1\mathrm{kJ}\mathrm{k}{\mathrm{g}}^{-1}{\mathrm{K}}^{-1}$ and $c_{\mathrm{water}}=4.18\mathrm{kJ}\mathrm{k}{\mathrm{g}}^{-1}{\mathrm{K}}^{-1}$, and latent heat of fusion $L_f=334\mathrm{kJ}\mathrm{k}{\mathrm{g}}^{-1}$. These are stipulated, rounded model values; ignore the container and heat losses, retain all the material, and assume only pressure-volume work under the quasistatic process conditions above. The three steps areOnly the first and third terms are sensible heat; the middle term is latent heat. The plateau begins after $10.5\mathrm{kJ}$ and ends after $177.5\mathrm{kJ}$ of total supplied heat. At $94\mathrm{kJ}$ total input, half the mass is liquid water and the temperature remains $0{}^{\circ }\mathrm{C}$. The equilibrium phase transition temperature depends on pressure; this example stipulates a single fixed pressure. ^[ref]

This split makes heating budgets easy to interpret: melting consumes $167/219.3\approx 76.2\%$ of the supplied heat in this model despite causing no temperature rise. Within either single thermodynamic phase, the heating curve slope is $dT/dQ=1/(m{c}_p)$; a larger heat capacity makes the slope shallower. A flat interval represents changing phase fraction, so it cannot be modeled by applying $Q=m{c}_p\Delta T$ across the phase transition. The complementary constructed example in latent heat tracks that phase fraction explicitly.

For the Landau free energy $G(\varphi )={\varphi }^6/6+g{\varphi }^4/4+\epsilon {\varphi }^2/2$, positive $g$ gives a continuous phase transition at $\epsilon =0$. For negative $g$, phase coexistence between the disordered global minimum $\varphi =0$ and the ordered global minima occurs on $\epsilon =3g^2/16$, with ${\varphi }^2=-3g/4$. Indeed, on that locus the polynomial is $G(\varphi )={\varphi }^2({\varphi }^2+3g/4{)}^2/6\ge 0$, so these three zeros are global minima. For $g<0$, the disordered and ordered spinodal points are respectively $\epsilon =0$ and $\epsilon =g^2/4$; equality of stationary free energies determines phase coexistence, while loss of a local minimum determines a spinodal point.

The thermodynamic limit describes a sequence of larger systems, not a single enormous specimen: particle number $N$ and volume $V$ tend to infinity with number density $n=N/V$ fixed. Hold the chosen intensive and extensive thermodynamic quantities such as temperature $T$ and an applied magnetic field fixed along that sequence. In the canonical ensemble the controls are $T,N,V$; in the grand canonical ensemble one instead fixes $T$ and chemical potential, and the limiting number density is a result, possibly with a jump at phase coexistence. These are different specifications of a limiting experiment.

The useful limit is usually an intensive and extensive thermodynamic quantities normalization of the Helmholtz free energy, not a finite limit of the total extensive quantity itself:Here $Z_{N,V}$ is the canonical partition function, $k_B$ is the Boltzmann constant, $f$ is free-energy density, and $a$ is Helmholtz free energy per particle. Thus $F_{N,V}=Vf+o(V)$ when the limit exists; finite systems need not be exactly extensive quantities because of the surface correction to thermodynamic free energy.

Specify the interactions and the growing containers too. For a conventional fluid, use a fixed stable pair potential with a tempered pair potential tail, and containers whose boundary layer of any fixed thickness occupies a vanishing fraction of the volume; uniformly enlarged cubes work, a tube of fixed cross-section does not give the same bulk limit. For a finite-range Ising model, keep the lattice spacing and bond coupling fixed while enlarging all intended spatial directions. Ordinary bounded wall interactions or periodic boundary conditions can then give the same bulk free-energy density, although boundary conditions can select different spontaneous symmetry breaking states. This is a set of hypotheses, not a theorem that every interaction has a boundary-independent limit.^[ref]

The Curie–Weiss model below deliberately uses a different limiting prescription: its all-to-all coupling is divided by $N$. Without that factor its interaction energy would grow as $N^2$, rather than as an extensive quantity. The model has no spatial wall or correlation length to compare with a container; it is an exactly summable illustration of finite-size rounding, not a quantitative model of the fluid experiment below.

A thermodynamic phase is a form of macroscopic equilibrium characterized by its structure, symmetries and thermodynamic response. Away from phase transitions, its free-energy density varies smoothly with the control parameters. Different phases can share a phase coexistence boundary. An ordered magnetic phase is distinguished from a disordered phase by its spontaneous order parameter; positive and negative ordered states are different pure thermodynamic phases related by spin inversion symmetry.

For an even sextic Landau free energy perturbed by a conjugate field, a tricritical wing is a phase coexistence surface at nonzero field between ordered minima of different magnitudes. Two symmetry-related wings emerge from the three-phase line at zero field and terminate at ordinary critical edges. They meet the zero-field ordered coexistence sheet at the tricritical point.